EP3587523A1 - Low oxide trench dishing chemical mechanical polishing - Google Patents

Low oxide trench dishing chemical mechanical polishing Download PDF

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Publication number
EP3587523A1
EP3587523A1 EP19183667.5A EP19183667A EP3587523A1 EP 3587523 A1 EP3587523 A1 EP 3587523A1 EP 19183667 A EP19183667 A EP 19183667A EP 3587523 A1 EP3587523 A1 EP 3587523A1
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EP
European Patent Office
Prior art keywords
group
ceria
organic
coated
combinations
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EP19183667.5A
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German (de)
English (en)
French (fr)
Inventor
Xiaobo Shi
Krishna P. Murella
Joseph D ROSE
Hongjun Zhou
Mark Leonard O'neill
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Versum Materials US LLC
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Versum Materials US LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1436—Composite particles, e.g. coated particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H01L21/3043—Making grooves, e.g. cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers

Definitions

  • This invention relates to chemical mechanical planarization (CMP) for polishing oxide and doped oxide films.
  • An important step in the fabrication of microelectronics devices is polishing, especially polishing of surfaces by chemical-mechanical polishing for the purpose of recovering a selected material and/or planarizing the structure.
  • a SiN layer is deposited under a SiO 2 layer to serve as a polish stop.
  • the role of such a polish stop is particularly important in Shallow Trench Isolation (STI) structures.
  • Selectivity is characteristically expressed as the ratio of the oxide polish rate to the nitride polish rate.
  • An example is an increased polishing selectivity rate of silicon dioxide(SiO 2 ) as compared to silicon nitride(SiN).
  • reducing oxide trench dishing is a key factor to be considered.
  • a lower trench oxide loss will prevent electrical current leaking between adjacent transistors.
  • Non-uniform trench oxide loss across die (within Die) will affect transistor performance and device fabrication yields.
  • Severe trench oxide loss high oxide trench dishing
  • US Patent 5,876,490 discloses polishing compositions containing abrasive particles and exhibiting normal stress effects.
  • the slurry further contains non-polishing particles resulting in reduced polishing rate at recesses, while the abrasive particles maintain high polish rates at elevations. This leads to improved planarization.
  • the slurry comprises cerium oxide particles and polymeric electrolyte, and can be used for Shallow Trench Isolation (STI) polishing applications.
  • STI Shallow Trench Isolation
  • US Patent 6,964,923 teaches the polishing compositions containing cerium oxide particles and polymeric electrolyte for Shallow Trench Isolation (STI) polishing applications.
  • Polymeric electrolytes that are used includes the salts of polyacrylic acid, similar as those in US Patent 5,876,490 .
  • Ceria, alumina, silica & zirconia are used as abrasives.
  • Molecular weight for such listed polyelectrolytes is from 300 to 20,000, but in overall, ⁇ 100,000.
  • US Patent 6,616,514 discloses a chemical mechanical polishing slurry for use in removing a first substance from a surface of an article in preference to silicon nitride by chemical mechanical polishing.
  • the chemical mechanical polishing slurry according to the invention includes an abrasive, an aqueous medium, and an organic polyol that does not dissociate protons, said organic polyol including a compound having at least three hydroxyl groups that are not dissociable in the aqueous medium, or a polymer formed from at least one monomer having at least three hydroxyl groups that are not dissociable in the aqueous medium.
  • compositions, methods and systems of chemical mechanical polishing that can provide reduced oxide trench dishing and improved over polishing window stability in a chemical and mechanical polishing (CMP) process, in addition to a high removal rate of silicon dioxide as well as high selectivity for silicon dioxide to silicon nitride.
  • the present invention provides Chemical mechanical polishing(CMP) compositions, methods and systems in CMP applications for polishing oxide films.
  • the present invention provides the benefits of achieving high oxide film removal rates, low SiN film removal rates, high and tunable Oxide: SiN selectivity, lower total defect counts post-polishing, and excellent mean particle size(nm) stability, and, importantly, significantly reducing oxide trench dishing and improving over polishing window stability.
  • a CMP polishing composition that comprises or consists of:
  • Suitable ceria-coated inorganic oxide particles include, but are not limited to, ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia, or any other ceria-coated inorganic oxide particles.
  • Suitable ceria-coated organic polymer particles include, but are not limited to, ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, or any other ceria-coated organic polymer particles.
  • the preferred abrasive particles are ceria-coated inorganic oxide particles; the most preferred abrasive particles are ceria-coated silica particles.
  • Suitable solvent include but are not limited to deionized (DI) water, distilled water, and alcoholic organic solvents.
  • the chemical additives contain at least one six-member ring structure motif ether bonded with at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures or at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures and at least one six-member ring polyol.
  • a polyol is an organic compound containing hydroxyl groups.
  • the chemical additives as oxide trenching dishing reducers contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structures.
  • At least one R in the group of R1 to R5 in the general molecular structure is a polyol molecular unit having a structure shown in (b): wherein n and m can be the same or different, wherein m and n are each independently selected from 1 to 5, preferably from 1 to 4, more preferably from 1 to 3, and most preferably from 1 to 2, and wherein R6 to R9 can be the same or different atoms or functional groups and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group with one or more hydroxyl groups, a substituted organic sulfonic acid or salt, a substituted organic carboxylic acid or salt, an organic carboxylic ester, an organic amine, and combinations thereof; and the rest of the Rs in the group of R1 to R5 are each independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group with one or more hydroxyl groups, a substituted organic
  • At least one R in the group of R1 to R5 in the general molecular structure is a polyol molecular unit having a structure shown in (b); at least one R in the group of R1 to R5 in the general molecular structure is a six-member ring polyol as shown in (c): wherein
  • At least two, preferably four, more preferably six of the Rs in the group of R1 to R9 are hydrogen atoms.
  • R2 is the six-member ring polyol
  • OR14 is replaced by O in the structure of (a) (specifically, the O in the structure of (a) that is connected to R2)
  • the preferred chemical additive comprises or consists of maltitol, lactitol, maltotritol, or combinations thereof.
  • the CMP polishing composition can be made into two or more parts and mixed at the point of use.
  • CMP chemical mechanical polishing
  • CMP chemical mechanical polishing
  • the polished oxide films can for example be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD(HDP), or spin on oxide films.
  • CVD Chemical vapor deposition
  • PECVD Plasma Enhance CVD
  • HDP High Density Deposition
  • spin on oxide films can for example be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD(HDP), or spin on oxide films.
  • the substrate disclosed above can further comprises a silicon nitride(SiN) surface.
  • the removal selectivity of SiO 2 : SiN is greater than 10, preferably greater than 20, and more preferably greater than 30.
  • This invention relates to Chemical mechanical polishing(CMP) compositions, methods and systems for CMP applications such as polishing oxide and doped oxide films.
  • CMP Chemical mechanical polishing
  • reducing oxide trench dishing is a key factor to be considered.
  • the lower trench oxide loss will prevent electrical current leaking between adjacent transistors.
  • Non-uniform trench oxide loss across die or/and within Die will affect transistor performance and device fabrication yields.
  • Severe trench oxide loss (high oxide trench dishing) will cause poor isolation of transistor resulting in device failure. Therefore, it is important to reduce trench oxide loss by reducing oxide trench dishing in CMP polishing compositions.
  • the CMP compositions comprise unique combinations of abrasive and the suitable chemical additives.
  • This invention provides reduced oxide trench dishing and thus improved over polishing window stability by introducing chemical additives as oxide trench dishing reducing additives in the Chemical mechanical polishing(CMP) compositions at wide pH range including acidic, neutral and alkaline pH conditions.
  • CMP Chemical Mechanical Polishing
  • the Chemical Mechanical Polishing (CMP) compositions also further provide excellent mean particle size and size distribution stability for the abrasive particles which is very important in maintaining robust CMP polishing performances with minimized polishing performance variations.
  • a CMP polishing composition that comprises or consists of:
  • the ceria-coated inorganic oxide particles include, but are not limited to, ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia, or any other ceria-coated inorganic oxide particles.
  • Suitable ceria-coated organic polymer particles include, but are not limited to, ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, or any other ceria-coated organic polymer particles.
  • the average mean particle sizes or mean particle sizes (MPS) of the abrasive particles in the disclosed invention herein are preferably ranged from 2 to 1,000nm, 5 to 500nm, 15 to 400 nm or 25 to 250nm.
  • MPS refers to diameter of the particles and is measured using dynamic light scattering (DLS) technology.
  • the concentrations of abrasive particles preferably range from 0.01 wt.% to 20 wt.%, 0.05 wt.% to 10 wt.%, or 0.1 wt.% to 5 wt.%.
  • all references to the wt.% of a component of a composition indicate the weight percent of that component by total weight of the composition.
  • the preferred abrasive particles are ceria-coated inorganic oxide particles; the most preferred abrasive particles are ceria-coated silica particles.
  • Suitable solvent include but are not limited to deionized (DI) water, distilled water, and alcoholic organic solvents.
  • the preferred solvent is DI water.
  • the CMP slurry may for example contain biocide from 0.0001 wt.% to 0.05 wt.%; 0.0005 wt.% to 0.025 wt.%, or 0.001 wt.% to 0.01 wt.%.
  • Suitable biocides include, but are not limited to, KathonTM, KathonTM CG/ICP II, from Dupont/Dow Chemical Co. Bioban from Dupont/Dow Chemical Co. They have active ingredients of 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.
  • the CMP slurry may contain a pH adjusting agent.
  • An acidic or basic pH adjusting agent can be used to adjust the polishing compositions to the optimized pH value.
  • Suitable acidic pH adjusting agents include, but are not limited to nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof.
  • Suitable basic pH adjusting agents include, but are not limited to sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkyl ammonium hydroxide, organic quaternary ammonium hydroxide compounds, organic amines, and other chemical reagents that can be used to adjust pH towards the more alkaline direction.
  • the CMP slurry may for example contain 0 wt.% to 1 wt.%; 0.01 wt.% to 0.5 wt.%; or 0.1 wt.% to 0.25 wt.% pH adjusting agent.
  • the CMP slurry preferably contains 0.01 wt.% to 20 wt.%, 0.025 wt.% to 10 wt.%, 0.05 wt.% to 5 wt.%, or 0.1 to 3.0% wt.% of the chemical additives as oxide trenching dishing and total defect count reducers.
  • the chemical additives contain at least one six-member ring structure motif ether bonded with at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures or at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures and at least one six-member ring polyol.
  • a polyol is an organic compound containing hydroxyl groups.
  • the chemical additives as oxide trenching dishing reducers contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structures.
  • At least one R in the group of R1 to R5 in the general molecular structure is a polyol molecular unit having a structure shown in (b): wherein n and m can be the same or different, wherein m and n are each independently selected from 1 to 5, preferably from 1 to 4, more preferably from 1 to 3, and most preferably from 1 to 2; and wherein R6 to R9 can be the same or different atoms or functional groups and each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group with one or more hydroxyl groups, a substituted organic sulfonic acid or salt, a substituted organic carboxylic acid or salt, an organic carboxylic ester, an organic amine, and combinations thereof; and the rest of Rs in the group of R1 to R5 are each independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group with one or more hydroxyl groups, a substituted organic
  • At least one R in the group of R1 to R5 in the general molecular structure is a polyol molecular unit having a structure shown in (b); at least one R in the group of R1 to R5 in the general molecular structure is a six-member ring polyol as shown in (c): wherein
  • At least two, preferably four, more preferably six of the Rs in the group of R1 to R9 are hydrogen atoms.
  • the preferred chemical additive comprises or consists of maltitol, lactitol, maltotritol, or combinations thereof.
  • the CMP polishing compositions can be made into two or more parts and mixed at the point of use.
  • CMP chemical mechanical polishing
  • CMP chemical mechanical polishing
  • the polished oxide films can be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD(HDP), spin on oxide films, flowable CVD oxide film, carbon doped oxide film, or nitrogen doped oxide film.
  • CVD Chemical vapor deposition
  • PECVD Plasma Enhance CVD
  • HDP High Density Deposition
  • spin on oxide films flowable CVD oxide film, carbon doped oxide film, or nitrogen doped oxide film.
  • the substrate disclosed above can further comprises a silicon nitride surface.
  • the removal selectivity of SiO 2 : SiN is greater than 10, preferably greater than 20, and more preferably greater than 30.
  • Dishing performance of the CMP compositions can also be characterized by the ratio of oxide trench dishing rate ( ⁇ /min.) vs the blanket HDP film removal rate( ⁇ /min.).
  • the CMP compositions having the ratio of ⁇ 0.1, 0.08, 0.06, 0.05, 0.03, or 0.02 provide good oxide dishing performance.
  • these chemical additives can have some impacts on the stability of abrasive particles in the compositions.
  • these chemical additives can have some impacts on the stability of ceria-coated inorganic oxide abrasives in the CMP polishing compositions.
  • the abrasive particle stability is tested by monitoring the mean particle size (MPS) (nm) and particle size distribution parameter D99(nm) changes vs the times or at elevated temperatures.
  • MPS mean particle size
  • Particle size distribution may be quantified as a weight percentage of particles that has a size lower than a specified size.
  • parameter D99(nm) represents a particle size (diameter) where 99 wt.% of all the slurry particles would have particle diameter equal to or smaller than the D99(nm). That is, D99(nm) is a particle size that 99 wt.% of the particles fall on and under.
  • Particle size distribution can be measured by any suitable techniques such as imaging, dynamic light scattering, hydrodynamic fluid fractionation, disc centrifuge etc..
  • MPS(nm) and D99 (nm) are both measured by dynamic light scattering in this application.
  • CMP compositions providing abrasive particle stability preferably have changes for MPS (nm) and D99(nm) ⁇ 6.0%, 5.0%, 3.0%, 2.0%, 1.0%, 0.5 %, 0.3% or 0.1% for a shelf time of at least 30 days, 40 days, 50 days, 60 days, 70 days or 100 days at a temperature ranging from 20 to 60 °C, 25 to 50 °C.
  • ⁇ or A angstrom(s) - a unit of length BP: back pressure, in psi units
  • CS carrier speed
  • DF Down force: pressure applied during CMP, units psi min: minute(s) ml: milliliter(s) mV: millivolt(s) psi: pounds per square inch
  • PS platen rotational speed of polishing tool, in rpm (revolution(s) per minute)
  • SF slurry flow, ml/min Wt.
  • TEOS SiN Selectivity: (removal rate of TEOS)/ (removal rate of SiN)
  • HDP high density plasma deposited TEOS TEOS or HDP Removal Rates: Measured TEOS or HDP removal rate at a given down pressure.
  • the down pressure of the CMP tool was 2.0, 3.0 or 4.0 psi in the examples.
  • SiN Removal Rates Measured SiN removal rate at a given down pressure.
  • the down pressure of the CMP tool was 3.0 psi in the examples.
  • ResMap CDE model 168, manufactured by Creative Design Engineering, Inc, 20565 Alves Dr., Cupertino, CA, 95014.
  • the ResMap tool is a four-point probe sheet resistance tool. Forty-nine-point diameter scan at 5mm edge exclusion for film was taken.
  • the CMP tool that was used is a 200mm Mirra, or 300mm Reflexion manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054.
  • An IC1000 pad supplied by DOW, Inc, 451 Bellevue Rd., Newark, DE 19713 was used on platen 1 for blanket and pattern wafer studies.
  • the IC1010 pad or other pad was broken in by conditioning the pad for 18 mins. At 7 lbs. down force on the conditioner. To qualify the tool settings and the pad break-in two tungsten monitors and two TEOS monitors were polished with Versum® STI2305 slurry, supplied by Versum Materials Inc. at baseline conditions.
  • Polishing experiments were conducted using PECVD or LECVD or HD TEOS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051.
  • oxide blanket wafers, and SiN blanket wafers were polished at baseline conditions.
  • the tool baseline conditions were: table speed; 87 rpm; head speed: 93 rpm; membrane pressure: 3.0 psi; inter-tube pressure: 3.1 psi; retaining ring pressure: 5.1psi; slurry flow speed: 200 ml/min.
  • the slurry was used to polish the patterned wafers (MIT860), supplied by SWK Associates, Inc. 2920 Scott Boulevard. Santa Clara, CA 95054). These wafers were measured on the Veeco VX300 profiler/AFM instrument. The 3 different sized pitch structures were used for oxide dishing measurement. The wafer was measured at center, middle, and edge die positions.
  • TEOS SiN Selectivity: (removal rate of TEOS)/ (removal rate of SiN) obtained from the CMP polishing compositions were tunable.
  • a reference (ref.)polishing composition comprising 0.2 wt.% ceria-coated silica, a biocide ranging from 0.0001 wt.% to 0.05 wt.%, and deionized water was prepared.
  • the polishing compositions were prepared with the reference (0.2 wt.% ceria-coated silica, a biocide ranging from 0.0001 wt.% to 0.05 wt.%, and deionized water) and a chemical additive ranging from 0.01 wt.% to 2.0% wt.%.
  • compositions in the examples except compositions used in different pH condition example had a pH at 5.35.
  • pH adjusting agent used for acidic pH condition and alkaline pH condition were nitric acid and ammonium hydroxide respectively.
  • Example 1 the polishing compositions were prepared as shown in Table 1.
  • the chemical additives, maltitol or lactitol were used at 0.28 wt.% respectively.
  • Table 1 The test results are listed in Table 1 and shown in Figure 1 .
  • Table 1 Effects of Maltitol or Lactitol on Film RR ( ⁇ /min.) & TEOS: SiN Selectivity Compositions TEOS Film RR ( ⁇ /min.) HDP Film RR ( ⁇ /min.) SiN Film RR ( ⁇ /min.) TEOS: SiN Selectivity 0.2% Ceria-coated Silica pH 5.35 3279 2718 349 9.4 0.2% Ceria-coated Silica + 0.28% Maltitol pH 5.35 2623 2639 46 57.0 0.2% Ceria-coated Silica + 0.28% Lactitol pH 5.35 2630 2547 55 47.8
  • Example 2 the polishing compositions were prepared as shown in Table 2.
  • the chemical additives, maltitol or lactitol were used at 0.28 wt.% respectively. All samples had a pH at 5.35.
  • Oxide trenching dishing for without/or with different over polishing times were tested.
  • test results are listed in Table 2 and shown in Figure 2 .
  • polishing compositions with the addition of the chemical additives, maltitol or lactitol afforded low oxide trench dishing on 100um pitch and 200um pitch respectively when 60 second or 120 second over polishing(OP) times were applied.
  • compositions provided significant oxide trench dishing reductions compared to the reference polishing composition which did not have the chemical additives, maltitol or lactitol.
  • Table 2 Effects of Maltitol or Lactitol on Oxide Trench Dishing vs OP Times (Sec.) Compositions OP Times (Sec.) 100um pitch dishing 200um pitch dishing 0.2% Ceria-coated Silica pH 5.35 Ref.
  • Table 3 lists the ratio of oxide trench dishing rate (A/min.) vs the blanket HDP film removal rate( ⁇ /min.).
  • Table 3 Compositions P100 Dishing Rate ( ⁇ /min.)/Blanket HDP RR (A/min.) P200 Dishing Rate ( ⁇ /min.)/Blanket HDP RR (A/min.) 0.2% Ceria-coated Silica pH 5.35 0.13 0.16 0.2% Ceria-coated Silica + 0.28% Maltitol pH 5.35 0.02 0.03 0.2% Ceria-coated Silica + 0.28% Lactitol pH 5.35 0.03 0.03
  • the CMP polishing compositions comprising chemical additives, such as maltitol or lactitol, and ceria-coated silica again showed much lower slope values comparing to those slope values obtained for the ceria-coated silica abrasive based reference sample.
  • Example 3 the trench oxide loss rates were compared for the polishing compositions using reference and working compositions comprising maltitol or lactitol
  • compositions were prepared as shown in Table 6.
  • the reference composition did not use any chemical additives.
  • the working compositions comprised 0.2 wt.% ceria-coated silica as abrasives, 0.28 wt.% lactitol as chemical additive, biocide, DI water, and a pH adjusting agent to provide different pH conditions.
  • test results are listed in Table 6 and shown in Figure 5 .
  • Oxide trenching dishing using compositions without/or with lactitol as chemical additive, at different over polishing times were also tested.
  • lactitol containing polishing composition at different pH conditions on the oxide trenching dishing vs over polishing times were observed.
  • test results are listed in Table 7 and shown in Figure 6 .
  • polishing compositions with the chemical additive lactitol provided low oxide trench dishing on 100um pitch and 200um pitch respectively when 60 second or 120 second over polishing times were applied at three different tested pH conditions
  • compositions with lactitol as an oxide trench dishing reducing agent provided significant oxide trench dishing reductions comparing to the reference polishing composition which did not use the chemical additive, lactitol.
  • Table 8 Compositions P100 Dishing Rate (A/min.)/Blanket HDP RR (A/min.) P200 Dishing Rate ( ⁇ /min.) /Blanket HDP RR (A/min.) 0.2% Ceria-coated Silica pH 5.35 0.13 0.16 0.2% Ceria-coated Silica + 0.28% Lactitol pH 5.35 0.03 0.03 0.2% Ceria-coated Silica + 0.28% Lactitol pH 7.0 0.05 0.06 0.2% Ceria-coated Silica + 0.28% Lactitol pH 8.0 0.06 0.08
  • compositions with chemical additive lactitol provided lower slopes of trench dishing vs the over polishing removal amounts which indicated a good over polishing window for maintaining low oxide trench dishing, even when more oxide film is removed in over polishing steps, at all three tested pH conditions.
  • the trench oxide loss rates were compared between the polishing compositions using lactitol (at different pH conditions) and the reference without using lactitol at pH 5.35.
  • Table 10 Effects of Lactitol at Different pH Conditions on Trench Loss Rates (A/min.) Compositions P100Trench Loss Rate ( ⁇ /sec.) P200Trench Loss Rate ( ⁇ /sec.) 0.2% Ceria-coated Silica pH 5.35 Ref.
  • polishing test results obtained at different pH conditions indicates that the disclosed CMP polishing compositions comprising the chemical additives can be used for wide pH range; for acidic, neutral or alkaline pH conditions.
  • the stability of ceria-coated silica abrasive particles in the compositions having chemical additives was monitored by measuring the change of the mean particles size and the change of particle size distribution D99.
  • the reference composition was prepared using 0.2 wt.% ceria-coated silica abrasive and very low concentration of biocide, and pH was adjusted to 5.35.
  • the working compositions were made using 0.2 wt.% or other wt.% ceria-coated silica abrasive, very low concentration of biocide, and varied concentrations of maltitol or lactitol as oxide trench dishing reducer and with pH adjusted to 5.35.
  • the abrasive particle stability tests on the polishing compositions were carried out at 50 °C for at least 10 days.
  • the MPS (nm) and D99(nm) of the abrasive particles were measured using dynamic light scattering (DLS) technology.
  • polishing compositions comprising more concentrated ceria-coated silica abrasives ( more than 0.2 wt. %) and more concentrated maltitol (more than 0.15 wt. %) as oxide trench dishing reducer.
  • 1.6 wt. % of the ceria-coated silica particles had MPS and D99 changes of less than 1.2% and less than 1.6 % respectively by day 42 at 50 °C in the composition having 1.2 wt. % of maltitol respectively..
  • 2.4 wt. % of the ceria-coated silica particles had MPS and D99 changes of less than 0.33 % and less than 0.23 % respectively by day 42 at 50 °C in the composition having 1.8 wt. % of maltitol respectively.
  • the abrasive particles were stable in the disclosed CMP polishing compositions.
  • the first sample was prepared using 0.5 wt.% calcinated ceria abrasives, 0.05 wt.% polyacrylate salt and low concentration of biocide.
  • the first sample was picked since it is a known polishing CMP composition comprised of calcinated ceria abrasives and polyacrylate salt as a chemical additive for dispersing and as a trench dishing reducer.
  • the second sample was prepared using 0.2 wt.% ceria-coated silica abrasives, 0.28 wt.% maltitol and low concentration of biocide; the third sample was prepared using 0.2 wt.% ceria-coated silica abrasives, 0.28 wt.% lactitol and low concentration of biocide; all three formulations had pH valued at 5.35.
  • the polishing compositions using ceria-coated silica particles as abrasives and either maltitol or lactitol as trench dishing reducing agent afforded significantly lower total defect counts on the polished TEOS and SiN wafers than the total defect counts obtained using a well-known polishing composition comprised of calcinated ceria abrasives and polyacrylate salt as chemical additive.
  • the CMP polishing compositions in the present invention provide reduced total defect counts through- and post-polishing.
  • the present invention includes the following Aspects 1 to 26:

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